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A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents

[Image: see text] The study tackles one of the challenges in developing platinum-free molecular electrocatalysts for hydrogen evolution, which is to seek for new possibilities to ensure large turnover numbers by stabilizing electrocatalytic intermediates. These species are often much more reactive t...

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Autores principales: Zelinskii, Genrikh E., Pavlov, Alexander A., Belov, Alexander S., Belaya, Irina G., Vologzhanina, Anna V., Nelyubina, Yulia V., Efimov, Nikolay N., Zubavichus, Yan V., Bubnov, Yurii N., Novikov, Valentin V., Voloshin, Yan Z.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6645064/
https://www.ncbi.nlm.nih.gov/pubmed/31457271
http://dx.doi.org/10.1021/acsomega.7b01088
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author Zelinskii, Genrikh E.
Pavlov, Alexander A.
Belov, Alexander S.
Belaya, Irina G.
Vologzhanina, Anna V.
Nelyubina, Yulia V.
Efimov, Nikolay N.
Zubavichus, Yan V.
Bubnov, Yurii N.
Novikov, Valentin V.
Voloshin, Yan Z.
author_facet Zelinskii, Genrikh E.
Pavlov, Alexander A.
Belov, Alexander S.
Belaya, Irina G.
Vologzhanina, Anna V.
Nelyubina, Yulia V.
Efimov, Nikolay N.
Zubavichus, Yan V.
Bubnov, Yurii N.
Novikov, Valentin V.
Voloshin, Yan Z.
author_sort Zelinskii, Genrikh E.
collection PubMed
description [Image: see text] The study tackles one of the challenges in developing platinum-free molecular electrocatalysts for hydrogen evolution, which is to seek for new possibilities to ensure large turnover numbers by stabilizing electrocatalytic intermediates. These species are often much more reactive than the initial electrocatalysts, and if not properly stabilized by a suitable choice of functionalizing substituents, they have a limited long-time activity. Here, we describe new iron and cobalt(II) cage complexes (clathrochelates) that in contrast to many previously reported complexes of this type do not act as electrocatalysts for hydrogen evolution. We argue that the most probable reason for this behavior is an excessive stabilization of the metal(I) species by perfluoroaryl ribbed groups, resulting in an unprecedented long-term stability of the metal(I) complexes even in acidic solutions.
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spelling pubmed-66450642019-08-27 A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents Zelinskii, Genrikh E. Pavlov, Alexander A. Belov, Alexander S. Belaya, Irina G. Vologzhanina, Anna V. Nelyubina, Yulia V. Efimov, Nikolay N. Zubavichus, Yan V. Bubnov, Yurii N. Novikov, Valentin V. Voloshin, Yan Z. ACS Omega [Image: see text] The study tackles one of the challenges in developing platinum-free molecular electrocatalysts for hydrogen evolution, which is to seek for new possibilities to ensure large turnover numbers by stabilizing electrocatalytic intermediates. These species are often much more reactive than the initial electrocatalysts, and if not properly stabilized by a suitable choice of functionalizing substituents, they have a limited long-time activity. Here, we describe new iron and cobalt(II) cage complexes (clathrochelates) that in contrast to many previously reported complexes of this type do not act as electrocatalysts for hydrogen evolution. We argue that the most probable reason for this behavior is an excessive stabilization of the metal(I) species by perfluoroaryl ribbed groups, resulting in an unprecedented long-term stability of the metal(I) complexes even in acidic solutions. American Chemical Society 2017-10-18 /pmc/articles/PMC6645064/ /pubmed/31457271 http://dx.doi.org/10.1021/acsomega.7b01088 Text en Copyright © 2017 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Zelinskii, Genrikh E.
Pavlov, Alexander A.
Belov, Alexander S.
Belaya, Irina G.
Vologzhanina, Anna V.
Nelyubina, Yulia V.
Efimov, Nikolay N.
Zubavichus, Yan V.
Bubnov, Yurii N.
Novikov, Valentin V.
Voloshin, Yan Z.
A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents
title A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents
title_full A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents
title_fullStr A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents
title_full_unstemmed A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents
title_short A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents
title_sort new series of cobalt and iron clathrochelates with perfluorinated ribbed substituents
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6645064/
https://www.ncbi.nlm.nih.gov/pubmed/31457271
http://dx.doi.org/10.1021/acsomega.7b01088
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